铬(Ⅵ)-谷胱甘肽配合物诱导小牛胸腺DNA变性的新表征方法

本文采用电化学方法对铬(Ⅵ)-谷胱甘肽(GSH)配合物诱导DNA变性进行表征,同时运用原子力显微镜(AFM)对DNA损伤变性过程进行可视化探测.结果表明:在pH=5.6的HAc-NaAc缓冲溶液中,DNA溶液中加入Cr(Ⅵ)-GSH配合物后进行循环伏安扫描,+0.20 V和0.00 V(vs SCE)处出现一对新的氧化还原峰,该氧化还原峰随Cr(Ⅵ)-GSH配合物浓度增加峰电流上升.DNA热变性和表面活性剂SDS变性实验进一步证明了该峰为DNA变性后的氧化还原峰,且变性DNA的峰信号在修饰电极上比裸金电极上更为灵敏.电化学动力学表明在30 min内配合物诱导DNA变性的程度随时间的上升而增加,并通过AFM观察了配合物作用下DNA断链的过程.     

蟹壳粉-铋修饰碳糊电极吸附测定污水中的Cr(Ⅵ)

以线性扫描伏安法研究了蟹壳粉-铋修饰碳糊电极上Cr(Ⅵ)的电化学行为及其吸附富集行为。天然蟹壳粉具有吸附富集铬酸根的作用,吸附过程遵循扩展Langmuir等温吸附模型。金属铋能够催化铬酸根的电化学还原,使其还原峰电流增加,峰电位发生负移,从而实现对Cr(Ⅵ)的电化学测定。优化的实验条件为:pH=2.6(Na2HPO4-柠檬酸),静止时间50 s,吸附时间20 min,沉积电位-0.5 V,扫速0.05 V/s。在优化实验条件下,存在两段线性范围,分别为1.0×10-8~1.0×10-6mol.L-1和1.0×10-5~1.0×10-3mol.L-1,检出限为1.0×10-8mol/L。干扰实验结果表明,Cr(Ⅲ)和SO42-离子对检测没有干扰。方法用于污水中铬(Ⅵ)的测定,加标回收率为94%~106%,相对标准偏差为3.1%。     

循环伏安法检测水中微量铬(Ⅵ)

在二苯基碳酰二肼分光光度法的基础上,利用Cr(Ⅵ)与过量的二苯基碳酰二肼(DPC)反应,通过剩余的DPC在玻碳电极上的电化学行为测得水中微量Cr(Ⅵ)的浓度,发展了一种新的检测Cr(Ⅵ)浓度的方法。实验结果显示,DPC在玻碳电极上的氧化峰电位和还原峰电位分别为0.16 V和-0.12 V。通过分析电化学反应过程,给出了可行的反应机理。DPC的氧化峰电流在1.85×10~(-8)~3.70×10~(-7)mol/L Cr(Ⅵ)浓度范围内呈良好的线性关系,相关系数R~2=0.9940,检测限为7.0 nmol/L。     

2,3,7-三羟基-9-(2-羟基)萘基荧光酮光度法测定环境样品中微量铬(Ⅵ)

研究了在阳离子表面活性剂溴化十六烷基三甲胺(CTMAB)存在下,有机显色试剂2,3,7-三羟基-9-(2-羟基)萘基荧光酮(2-HNF)与Cr(Ⅵ)的显色反应和光度性质。结果表明,在pH=7.30的Na2HPO4-KH2PO4缓冲介质中,30min内可反应完全,2-HNF与Cr(Ⅵ)形成摩尔比为2∶1的紫红色络合物,络合物至少能稳定存在12h,其最大吸收波长位于570nm处,表观摩尔吸光系数为1.07×105L·mol-1·cm-1,Cr(Ⅵ)含量在0～1.40μg/5mL范围内符合比耳定律。该分析方法已用于环境样品中微量铬的测定,结果满意。     

铬(Ⅵ)与谷胱甘肽作用及其中间态配合物形成的电化学表征

本文采用电化学方法，对谷胱甘肽(GSH)与重铬酸钾的相互作用及其中间态配合物的形成过程进行研究。结果表明：在pH=5.6的HAc-NaAc缓冲溶液中，GSH浓度为Cr(Ⅵ)浓度5倍以上时，Cr(Ⅵ)与GSH作用完全并形成一新的中间态配合物，该中间态配合物于+0.21 V和+0.36 V(vs SCE)处产生一对新的氧化还原峰，UV-Vis的吸收光谱进一步证明了中间态配合物的形成。该配合物不稳定，在一定时间内缓慢分解，其电化学与UV-Vis光谱动力学信息同步。进一步探讨了GSH与Cr(Ⅵ)作用的电极反应机理。当Zn(Ⅱ)存在于该体系时，Zn(Ⅱ)对中间态配合物的生成和分解过程起着双向催化作用。     

8-羟基喹啉在ETAAS和ETV-ICP-AES测定铬形态中基体改进作用的比较研究

比较了8-羟基喹啉(8-Ox)在ETAAS和ETV-ICP-AES中的基体改进作用。结果表明：在ETAAS中，8-Ox无论是对Cr(Ⅲ)还是对Cr(Ⅵ)都表现出良好的化学改进作用。而在ETV-AES中，8-Ox只对Cr(Ⅲ)有化学改进作用，借此可实现Cr(Ⅲ)和Cr(Ⅵ)的原位分离。     

电化学传感分析平台测定污水中的Cr（Ⅵ）

结合微型电化学仪器,研究了一种快速、便携、灵敏的Cr(Ⅵ)电化学传感分析平台,用于污水中Cr(Ⅵ)的检测。采用三电极体系,差分脉冲阴极溶出伏安法(DPCSV),记录伏安曲线中Cr(Ⅵ)的还原峰。Cr(Ⅵ)的溶出峰电流与其浓度在2～500μmol/L范围内有良好的线性关系,测得Cr(Ⅵ)的检出限为0.55μmol/L (28.60μg/L),达到了世界卫生组织(WHO)规定的饮用水中Cr(Ⅵ)的最高含量50μg/L。测得镀铬厂废水中Cr(Ⅵ)含量为2.03μmol/L,与国家标准方法中光谱学分析法的测定结果基本一致。方法重现性好、灵敏度高,使其应用在现场实时监测环境中的Cr(Ⅵ)含量具有很大的潜力。     

二安替比林基-4-羟基苯基甲烷及其与铬(Ⅵ)显色反应的研究

合成了二安替比林基-4-羟基苯基甲烷(DApHM),研究了它与铬(Ⅵ)的显色反应,建立了两个测定铬(Ⅵ)的新体系.在Mn(Ⅱ)和磷酸存在下,DApHM与 Cr(Ⅵ)反应生成橙红色产物,λ_max为435nm.CTMAB和Tween-80对该体系有明显增敏效果,其中CTMAB-DApHM-Cr(Ⅵ)体系ε为1.0 ×10~6;Tween-80-DApHM-Cr(Ⅵ)体系ε为6.9×10~5.Cr(Ⅵ)量在0.1～0.7μg/25mL间符合比尔定律.用于电镀废液和自来水中Cr(Ⅵ)的测定,结果满意.     

基于AuNPs/PANI-NF复合膜的电化学细胞传感器对姜黄素诱导HeLa细胞凋亡的抑制作用检测

以聚苯胺纳米纤维(PANI-NF)-纳米金(AuNPs)复合膜构建传感界面,在AuNPs/PANI-NF界面上修饰转铁蛋白(Tf),利用转铁蛋白与人宫颈癌细胞(HeLa)表面大量表达的转铁蛋白受体(TfR)之间的特异性识别作用,将细胞捕获到传感器界面,导致电化学阻抗值变化。利用电化学阻抗谱研究姜黄素对HeLa细胞的抑制作用。结果表明,随着药物浓度的增大和作用时间的延长,电化学阻抗值下降,表明姜黄素对细胞的抑制作用增强。电化学阻抗值的变化率与药物浓度和作用时间具有量效关系;电化学方法检测显示,姜黄素对HeLa细胞的抑制作用趋势与MTT法及倒置显微镜检测到的姜黄素对HeLa细胞的抑制作用结果相吻合,从而建立了一种检测药物对细胞抑制作用的新方法。该方法具有简便、灵敏度高、费用低廉等优点。     

PPS基叔胺离子交换纤维对Cr(Ⅵ)选择性吸附研究

首次报道通过氯甲基化聚苯硫醚纤维的胺化反应制得一种叔胺型离子交换纤维,研究了Cr2O72-和SO42-共存体系中该纤维对Cr(Ⅵ)的选择性吸附性能。结果表明,该离子交换纤维具有很高吸附容量,SO42-的存在并不影响该纤维对Cr(Ⅵ)的选择性吸附。在溶液pH值为2,Cr(Ⅵ)和SO42-浓度分别为65mg/L和480mg/L条件下,OH-型和SO42-型叔胺离子交换纤维对Cr(Ⅵ)的吸附容量分别为308.09mg/g和335.56mg/g。NaOH溶液可将CrO42-有效洗脱,纤维经过5次吸附-再生循环后,其吸附性能基本保持不变。     

利用手持技术改进测定乙醇分子结构实验

利用压强传感器代替排水集气法,改进测定乙醇分子结构实验的仪器装置,并探索最佳反应条件。另外,设计两个空白实验,结合压强变化曲线对实验误差进行相关讨论。     

Neutral diterpenoids of oleoresins of five species of conifers of Transcarpathia

The compositions of the neutral diterpenoids of the oleoresins of five species of conifers growing in the Transcarpathia have been studied. It has been found that the oleoresins ofAbies alba M.,Larix decidua M., andPicea excelsa L. contain more than 50% of neutral diterpenoids. The group and qualitative compositions of the oxygen-containing diterpenoids have been determined. In the oleoresins ofAbies alba,Picea excelsa, andPicea abies tertiary alcohols — cis-abienol and isocembrol — predominate, while inLarix decidua the main component is the hydroxy ester larixyl acetate. Primary alcohols related to the resin acids have been found in all the oleoresins investigated. Features of the distribution of diterpenoids according to the species of conifers have been revealed. The results obtained are necessary for the chemotaxonomy of conifers of the family Pinceae.Novosibirsk Institute of Organic Chemistry, Siberian Branch, Academy of Sciences of the USSR. Translated from Khimiya Prirodynkh Soedinenii, No. 6, pp. 812–816, November–December, 1988.     

光谱仪测试范围的扩展

由于石化行业的生产需要，其材质的使用具有多样性和广泛性，经常会出现顾客委托的测试样品的一个或几个元素跨越光谱仪现有测试程序测量范围的情况。本法通过对光谱仪测试原理的认识，根据光谱仪的测试能力及标样的采集，实现了一个或几个元素测量范围的扩展，并对其测量的影响因素进行了研究。     

Dichroism of absorption and polarization of phosphorescence of molecules of the closed form of nitrobenzospirothiopyran

The spectral-polarization characteristics of absorption and phosphorescence of molecules of the initial form of nitro-substituted indolinospirobenzothiopyran were studied in oriented polyethylene films and in solutions with different polarity. An oscillator model of the electron transitions responsible for the formation of absorption and luminescence spectra was suggested. It was established that the principal differences in the spectral and photophysical properties of the compound studied and its oxygen-containing analog are associated with the fact that the electronegativity of the S atom is lower than that of the O atom. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1143–1146, June, 1997.     

Influence of viscosity of medium on processes of oxygen quenching of excited states of mesoporphyrin

The oxygen quenching rate constants for singlet and triplet excited states of the dimethyl ester of mesoporphyrin IX increase with decreasing viscosity of the medium and reach a maximum at a viscosity of approximately 0.4 mPa·sec, after which the rate constants begin to decrease. The drop in rate constant with increasing fluidity of the medium may be related to a nonequilibrium character of the elementary act in the interaction of the reactants in the solvent cage. In viscous media such as isopropyl alcohol, isobutyl alcohol, and isoamyl alcohol, the reaction radius is greater than the sum of the radii of the reacting particles. The long-range character of these processes is due to the relatively weak dependence of the quenching probability on distance.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 25, No. 2, pp. 161–167, March–April, 1989.     

Determination of heats of detonation and influence of components of composite explosives on heats of detonation of high explosives

The heats of detonation of 20 simple high explosives and explosive mixtures were determined by means of an adiabatic detonation calorimeter designed by the authors. The results indicated that the performance of the instrument was reliable and the experimental data were very accurate. For explosive mixtures, there was a linear accumulative relationship between the heats of detonation of the explosive mixture and its components. Accordingly, the heats of detonation of explosive mixtures could be calculated directly from the heats of detonation of simple explosives and the characteristic heats of other components. The experiments showed that the gold or brass shell of the cylindrical charge could be substituted by a thick-walled porcelain shell, which had the advantage of cheapness.

     

物质分配系数的测定实验改进

实验教学目的是从解决实际问题出发,以实验技术训练和实验设计思想培养为目标。介绍了将单一的物质分配系数测定实验改进为综合实验,提高了实验效果及实验资源利用率。     

Calculation of enthalpies of hydrogenation of hydrocarbons

Sets of hydrogen molecule equivalents have been developed which permit the calculation of hydrogenation of different types of carbon-carbon bonds from ab initio total energies (3-21G and 6-31G* basis sets, and, to a more limited extent, for MP2/6-31G* data) of reactants and products. The calculated enthalpies of hydrogenation are in good agreement with experiment for unstrained molecules, with average errors on the order of 2 kcal/mol. The 6-31G* equivalents allow the enthalpies for strained molecules to be calculated accurately, but the 3-21G equivalents do not. The equivalents for both basis sets have been tested by calculating the enthalpies of hydrogenation of carbon-carbon bonds in nitrogen- and oxygen-containing organic molecules, free radicals, and classical carbocations. The results are in good agreement with experiment in most cases.     

非那雄胺合成工艺改进

非那雄胺能抑制5α-还原酶的活性,明显降低二氢睾酮水平,是一种治疗良性前列腺增生的有效药品。该合成工艺以甾烯酮酸为原料,将其与氯化亚砜反应,无须分离即与叔丁胺反应得17β-酰胺化合物,再氧化开环,环合,氢化,脱氢合成了非那雄胺。经元素分析、IR、1HNMR、13CNMR、MS分析表征了其结构。该法无须使用昂贵的2,2-二吡啶二硫化物和剧毒药品苯亚硒酸酐,且以乙酸铵代替氨气,降低了对设备的要求和腐蚀,更适用于工业生产。